Method for controlling catalytic distillation etherifications

ABSTRACT

A process for the etherification of isoolefins with alcohols is provided wherein the reaction occurs simultaneously with separation of the ether product and reactants. To assure proper alcohol concentration in a catalytic distillation column, the oxygen concentration derived from alcohol is measured at a point below the catalyst bed and controlled to that which maximizes ether production while preventing alcohol from leaving the reactor with ether product.

This application is a continuation of application Ser. No. 08/011,464 filed Jan. 27, 1993, now abandoned, which is a continuation-in-part of application Ser. No. 964,496 filed Oct. 21, 1992 and now U.S. Pat. No. 5,248,837.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to the etherification of isoolefins, particularly C₄ and C₅ isoolefins, with an alcohol such as methanol, ethanol or mixtures thereof, to produce the corresponding tertiary ethers. More particularly the invention relates to a process wherein a catalytic distillation process is used in the process and wherein the concentration of the alcohol below the catalyst bed is controlled to prevent the concentration of the alcohol from becoming too low (and thus reducing the conversion) or too high (and thus contaminating the ether product).

2. Related Information

The reaction of an alcohol and an olefin and concurrent separation of the reactants from the reaction products by fractional distillation has been practiced for some time. The process is variously described in U.S. Pat. Nos. 4,232,177; 4,307,254; 4,336,407; 4,504,687; 4,987,807; and 5,118,873 all commonly assigned herewith.

Briefly the alcohol and isoolefin are fed to a distillation column reactor having a distillation reaction zone containing a suitable catalyst, such as an acid cation exchange resin, in the form of catalytic distillation structure, and also having a distillation zone containing inert distillation structure. As embodied in the etherification of iC₄ ⁼ 's and/or iC₅ ⁼ 's with methanol the olefin and an excess of methanol is first fed to a fixed bed reactor wherein most of the olefin is reacted to form the corresponding ether, methyl tertiary butyl ether (MTBE) or tertiary amyl methyl ether (TAME) . The fixed bed reactor is operated at a given pressure such that the reaction mixture is at the boiling point, thereby removing the exothermic heat of reaction by vaporization of the mixture. The fixed bed reactor and process are described more completely in U.S. Pat. No. 4,950,803 which is hereby incorporated by reference.

The effluent from the fixed bed reactor is then fed to the distillation column reactor wherein the remainder of the iC₄ ⁼ 's or iC₅ ⁼ 's are converted to the ether and the methanol is separated from the ether which is withdrawn as bottoms. The C₄ or C₅ cut generally contains about 10 to 60 per cent olefin, the remainder being inerts which are removed in the overheads from the distillation column reactor.

As noted above in the etherification of olefins with an alcohol there is preferably an excess of the alcohol available in the reactor. This means that there is an excess of methanol in the reaction distillation zone of the distillation column reactor. In the distillation column reactor the alcohol forms a minimum boiling azeotrope with either of the olefins. In the case of C₄ 's and methanol the azeotrope is only slightly more volatile than the C₄ 's, and therefore the methanol tends to remain in a relatively constant concentration with the C₄ 's throughout the column. Because the concentration of the methanol in the C₄ azeotrope is only about 4% (depending upon the composition of the C₄ mixture), it is necessary to operate with a methanol concentration somewhat below 4% to avoid exceeding the azeotrope, in which case the, excess will first accumulate in the column and then leave with the MTBE bottoms.

In the case of the C₅ 's, the azeotrope contains about 12 wt% methanol or about 8 wt% ethanol, and the boiling point of the azeotrope is 10 to 15 degrees F. below that of the corresponding C₅ 's. Thus, if the net flow of alcohol into the column (allowing for that reacting in the column) is less than the azeotrope concentration in the distillate, the alcohol concentration in the reaction distillation zone will be relatively quite low, about 1%. If the net alcohol flow into the column is higher than the azeotrope, the alcohol concentration will increase (60% has been measured) until alcohol leaves with the ether bottoms product. Neither case is desirable, because at low alcohol concentration the conversion of isoamylene to ether is low, whereas at high alcohol concentrations the ether purity is affected by the presence of the excess alcohol.

In addition to the considerations of azeotopes discussed above, when two or more different alcohols are fed at the same time, other factors affect the operation of the etherification. For example, in the case of etherification of iC₅ ⁼ with a mixed methanol/ethanol stream to produce TAME and tertiary amyl ethyl ether (TAEE) , there are two different azeotropes. The first is methanol with the C₅ 's which is 12% methanol. The second is the azeotrope between the C₅ 's and the ethanol which is 8% ethanol. The different alcohols also react at different rates with the isoolefins, e.g., methanol reacts more rapidly than ethanol with isopentenes.

It as an advantage of the present invention that the alcohol-hydrocarbon azeotrope is maintained throughout essentially all of the reaction distillation zone, maximizing conversion of the reactive olefins.

It is a second advantage of the present invention that the control of the alcohol concentration in the liquid leaving the reaction distillation zone insures an alcohol free ether product.

It is another advantage that a truncated alcohol concentration profile improves controllability of the column.

Finally, it is another advantage that the concentration of either methanol or ethanol is controlled by a single variable to assure adequate alcohol concentration and an alcohol free product.

SUMMARY OF THE INVENTION

The present invention is a method for controlling etherification reactions in catalytic distillation column reactor comprising maintaining the concentration of oxygen derived from alcohol in the range of greater than 0 weight % to less than 7 weight %, preferably in the range of 1 to less than 4 weight %, and more preferably more than 2 weight % measured at the lower end of the catalytic distillation zone or below the catalytic distillation zone in the column. Preferably the control is maintained at the "mid-reflux" point in the column, which is understood to mean herein the liquid below the catalytic distillation zone and above the bottoms exit of the column.

Surprisingly, it was discovered that when running a reaction distillation column for the production of ethers from the reaction of isoolefins and alcohol, that the alcohol concentration in the reaction may be controlled by the measuring the total oxygen derived from alcohol in the ranges specified, whether the alcohol comprises a single alcohol or a mixture of alcohols. This single control feature is unexpected because of the complex azeotropes and reaction rates that occur when multiple reactants are present.

It is highly desirable to maintain active, dynamic control of the alcohol within the column on a continuous basis. To this end an on line analyzer is provided which continuously measures and controls the total concentration of oxygen derived from alcohol at the mid reflux point within the column by adjusting the total alcohol feed to the unit.

In a specific embodiment it was discovered that when running a reaction distillation column for the combined production of TAME and TAEE from the reaction of isoamylenes with a mixed stream of methanol and ethanol that controlling the total oxygen content derived from alcohols is sufficient to achieve the desired results.

In one embodiment the total alcohol feed to the fixed bed reactors is adjusted in response to the measured alcohol concentration in the column. In another embodiment the alcohol feed is split into two streams, one going to the fixed bed reactor and the other to the column, either directly or mixed into the feed stream from the primary reactor. In a preferred embodiment the analyzer is of the infrared or near infrared variety because of its rapid response to changes in concentration.

In a specific embodiment wherein a mixed methanol/ethanol feed is used the alcohol feed stream is split as in the second embodiment utilizing an infrared type analyzer.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a simplified flow diagram of one embodiment of a process utilizing the invention.

FIG. 2 is a simplified flow diagram of a second embodiment of a process utilizing the invention.

FIG. 3 is a graphical presentation of the methanol concentration profile within a distillation column reactor utilizing the invention.

FIG. 4 is graphical presentation of the individual alcohol concentrations in the mid-reflux in a methanol and methanol/ethanol etherification reaction.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

U.S. Pat. Nos. 5,003,124 and 4,950,803 disclose a liquid phase process for the etherification of C₄ and C₅ isoolefins with C₁ to C₆ alcohols in a boiling point fixed bed reactor that is controlled at a pressure to maintain the reaction mixture at its boiling point which may be directly attached to a catalytic distillation reactor.

The catalytic distillation process employs a catalyst system (See U.S. Pat. Nos. 4,215,011 and 4,302,356) which provides for both reaction and distillation concurrently in the same reactor, at least in part within the catalyst system. The method involved is briefly described as one where concurrent reaction and distillation occur in combination reactor-distillation structures which are described in several U.S. Patents, namely U.S. Pat. Nos. 4,242,530; 4,250,052; 4,232,177; 4,302,356; 4,307,254; and 4,336,407. Additionally U.S. Pat. Nos. 4,302,356 and 4,443,559 disclose catalyst structures which are useful as distillation structures.

In the system and procedure for TAME production, methanol and isoamylene (or the stream from the boiling point reactor which contains, ether, some unreacted isoolefin and methanol or make up methanol) containing C₅ stream are continuously fed to the reactor/distillation column where they are contacted in the catalytic distillation structure. The methanol preferentially reacts with isoamylene, forming TAME which is heavier than the C₅ components of the feed and the methanol, hence it drops in the column to form the bottoms. Concurrently, the unreacted C₅ 's (e.g. n-pentane, n-pentenes) are lighter and form an overhead.

Similarly, when ethanol is included in the alcohol feed, both the methanol and ethanol preferentially react with isoamylene forming TAME and TAEE which are heavier than the C₅ components of the feed and the methanol and ethanol, hence they both drop in the column to form bottoms.

Catalysts preferred for the etherification process are cation exchangers, which contain sulfonic acid groups, and which have been obtained by polymerization or copolymerization of aromatic vinyl compounds followed by sulfonation.

The resulting products preferably contain an average of 1.3 to 1.8 sulfonic acid groups per aromatic nucleus. Particularly, suitable polymers which contain sulfonic acid groups are copolymers of aromatic monovinyl compounds with aromatic polyvinyl compounds, particularly, divinyl compounds, in which the polyvinyl benzene content is preferably 1 to 20% by weight of the copolymer (see, for example, German Patent specification 908,247).

The ion exchange resin is preferably used in a granular size of about 0.25 to 1 mm, although particles form 0.15 mm up to about 1 mm may be employed.

The resin catalyst is loaded into the fixed bed reactor as a fixed bed of the granules. The feed to the reaction is fed to the bed in liquid phase. The bed may be horizontal, vertical or angled. Preferably the bed is vertical with the feed passing downward through the bed and exiting, after reaction, through the lower end of the reactor.

A preferred catalytic distillation structure for use herein comprises placing the cation exchange resin particles into a plurality of pockets in a cloth belt, which is supported in the distillation column reactor by open mesh knitted stainless steel wire by twisting the two together in a helical form. This allows the requisite flows and prevents loss of catalyst. The cloth may be any material which is inert in the reaction. Cotton or linen are useful, but fiber glass cloth or "Teflon" cloth are preferred. The catalytic distillation structure when loaded into the column constitutes a distillation reaction zone.

Directly below the distillation reaction zone is a distillation zone containing inert distillation structure to effect the separation of unreacted alcohol from the ether product. A Model PA Infra Red Analyzer (IRA) obtained from ABB Process Analytics, Inc. is installed to sample and analyze the alcohol concentration of the liquid leaving the distillation reaction zone (in catalytic distillation terminology the mid-reflux). The IRA can be connected to either the primary alcohol flow control loop, injecting ahead of the fixed bed reactor, or to a secondary alcohol control loop which injects to the fixed bed reactor effluent and to the distillation column reactor directly. Both systems have been successfully tested, but the secondary alcohol control provides faster and more responsive control.

On a commercial scale the sample point should be connected close to the "mid-reflux stream" or the "froth valve" if operating in the mode described in U.S. Pat. Nos. 4,978,807 and 5,120,404 which are hereby incorporated by reference. For the secondary alcohol control scheme, a small stream of the alcohol, 5-10% of the total alcohol requirement will bypass the fixed bed reactor (primary reactor). The flow of this alcohol will be set by a flow controller and reset by the IRA controller. If the secondary alcohol flow approaches its maximum or minimum the flow of the primary alcohol will be adjusted to compensate. For optimal performance of the reaction distillation column the alcohol concentration in the mid-reflux stream should be between 4-8 percent where the feed is a C₅ stream and slightly lower when the feed is a C₄ or mixed C₄ /C₅ feed and the alcohol used is methanol.

Referring now to FIG. 1 there is shown a simplified flow diagram of a TAME process utilizing primary methanol control. Methanol is fed by pump 18 through flow line 1. The C₅ 's are fed via flow lines 2 and 3 respectively and combined with the methanol in flow line 8 as feed to two fixed bed reactors 20A and 20B containing the cation exchange resin packing 30A and 30B as described above. The effluent from the last fixed bed reactor 30B is fed to a distillation column reactor 10 having a distillation reaction zone 40 in the upper portion. The unreacted isoamylenes remaining in the effluent react in the distillation reaction zone 40 with methanol to form tertiary amyl methyl ether (TAME) which is removed as bottoms via flow line 5. Distillation zone 50 is provided below the distillation reaction zone to separate the unreacted methanol from the TAME. If desired the liquid flowing down the column may be restricted to provide a froth within the distillation reaction zone as described in U.S. Pat. No. 4,978,807. Unreacted methanol and lighter inerts are removed as overheads via flow line 7. Preferably a portion of the overheads is condensed and returned as reflux via flow line 6.

A Model PA Infra Red Analyzer 70 provided by ABB Process Analytics, Inc. is installed to sample and analyze the methanol concentration of the liquid (mid-reflux) as it leaves the reaction distillation zone 40. The IRA is operably connected to flow control loop 80 which controls flow control valve 90. The methanol feed rate is controlled such that the concentration in the mid-reflux is between 4-8%.

Referring now to FIG. 2 a simplified flow diagram of the secondary methanol control scheme is shown. The equipment and flow are essentially the same as in FIG. 1 except a slip stream 1A of methanol is removed from flow line 1 before control loop 92. A second control loop 92A is located in flow line 1A which responds to the IRA 70 controlling the flow of methanol through flow line 1A directly to the distillation column reactor. If the flow through flow line 1A approaches either the minimum or maximum flow control loop 92 is reset to compensate by adding or reducing the primary methanol feed rate.

Referring now to FIG. 3 there is shown a comparison of the methanol concentration profiles when there is insufficient methanol feed, excess methanol feed, and when the methanol feed is controlled by the mid-reflux concentration at about 8 per cent. As may be seen, when there is a shortage of methanol feed, there is only about 4-8 per cent excess methanol in the reaction distillation zone. It has been noted that such a profile reduces the conversion of the isoolefins by up to 30%.

While the methanol concentration profile in the reaction distillation zone is adequate when excess methanol is fed, there is about 3 per cent methanol in the bottoms TAME produce. When the methanol concentration in the mid-reflux (liquid leaving the distillation reaction zone) is controlled at about 8 per cent the same profile in the reaction distillation zone is achieved as with excess methanol feed. However, there is no methanol in the bottoms.

While the control scheme has been shown primarily for the production of TAME the same scheme could be used in the MTBE process. This would be especially useful wherein the C₄ feed stream includes a high concentration of the reactive iC₄ ⁼. The high concentration of the iC₄ ⁼ requires balancing a large methanol feed flow with the demands of the entire system. The analyzer and control system would be very advantageous in preventing excess or shortage of methanol.

Another process which is benefitted by the use of the analyzer control scheme is a process which feeds a combined C₄ /C₅ stream and produces TAME and MTBE.

A final use of the control scheme is in the production of TAME/TAEE by reacting isoamylenes with a mixed stream of alcohol such as methanol and ethanol. Various mixtures of C₁ to C₆ alcohols may be used, such as methanol/propanol, methanol/isopropanol, ethanol/propanol, ethanol/isopropanol, methanol/butanol, methanol/tertiary butanol, ethanol/butanol, ethanol/tertiary butanol, methanol/ethanol/propanol, methanol/isopropanol/tertiary butanol, ethanol/propanol/isopropanol, and the like.

Surprisingly, it has been found that the individual alcohol concentrations need not be monitored and controlled. It is sufficient to monitor the total oxygen concentration based on oxygen derived from alcohol. The on-line analyzer is calibrated to read wt% oxygen derived from alcohols. Thus for the methanol/ethanol mixture the total oxygenate as alcohol is:

    % Oxygen from alcohols=(wt% MeOH/32+wt% EtOH/46)×16.

When the analyzer is so calibrated, the total alcohol concentration in the mid-reflux bed can be controlled to prevent the alcohols from exiting with the ether bottoms.

Methanol and ethanol are frequently found in the same stream. The set point is selected such that this occurs with any combination of MeOH/EtOH which is generally in the range of 0.5 wt% to 7 wt% oxygenates from alcohol, preferably 2 wt% to 3 wt%.

Table I below presents data from two test runs wherein the pilot plant was configured as in FIG. 2 except that a mixed methanol/ethanol stream was fed in lieu of methanol only.

Run B differs from Run A in that during Run A the mixed methanol/ethanol was fed the entire time. During Run B the unit was started with methanol only and ethanol added after about 100 hours. The unit was lining out and was approaching equilibrium at 192 hours or about 100 hours after the ethanol was first added. This established that the alcohol in the bottoms would soon cease. This portion of the run was terminated by ending the ethanol feed and returning to pure methanol feed. The alcohol feed for run B is visually depicted by FIG. 4.

During both runs the isoamylene conversion was satisfactory and no attempt was made to find the lower limit to starve either of the reactions. The total oxygen (derived from alcohol) below the catalyst bed must be above zero or the reactions would be starved and conversion to TAME/TAEE would fall off.

                  TABLE I                                                          ______________________________________                                         Time on Stream, hrs                                                                           O.sub.2.sup.1 in MRFLX                                                                     EtOH in Btms                                        ______________________________________                                         RUN A                                                                           8             0.83        0.000                                                20            2.86        0.011                                                32            3.02        0.000                                                44            1.20        0.000                                                66            2.96        0.508                                               RUN B                                                                          108            3.06        5.829                                               120            3.37        6.781                                               132            3.09        6.245                                               144            3.02        6.291                                               156            2.51        6.007                                               180            2.57        0.489                                               192            2.69        0.138                                               ______________________________________                                          .sup.1 Derived from alcohol                                               

The invention claimed is:
 1. In a process for the production of ethers from the reaction of isoolefins with a mixture of alcohols in a distillation column reactor having a distillation reaction zone above a distillation zone, the improvement comprising determining the concentration of oxygen derived from alcohol at the lower end of or a point below the distillation reaction zone and maintaining the concentration of the oxygen in the range of greater than 0 weight % to 7 weight %.
 2. The process according to claim 1 wherein the oxygen derived from alcohol is maintained in the range of 1 to less than 7 weight %.
 3. The process according to claim 1 wherein the oxygen derived from alcohol is maintained in the range of more than 2 weight % to 3 weight %.
 4. The process according to claim 1 wherein said mixture of alcohol is a mixed stream of methanol and ethanol.
 5. The process according to claim 4 wherein said isoolefin is isoamylene.
 6. The process according to claim 5 wherein said oxygen concentration derived from alcohol in the liquid directly below said distillation reaction zone is controlled below about 3 wt %.
 7. The process according to claim 3 wherein said oxygen concentration derived from alcohol in the liquid directly below said distillation reaction zone is controlled above 2 wt %.
 8. The process according to claim 1 wherein the oxygen concentration derived from alcohol is controlled by measuring the concentration by an infrared analyzer.
 9. The process according to claim 1 wherein said alcohols are selected from C₁ To C₆ alcohols.
 10. The process according to claim 1 wherein said alcohols are selected from methanol, ethanol, propanol, isopropanol, butanol or tertiary butanol.
 11. A process for the production of tertiary amyl methyl ether and tertiary amyl ethyl ether comprising the steps of:(a) feeding a first stream containing C₅ hydrocarbons including isoamylenes to a fixed bed straight pass reactor containing an acid cation exchange resin catalyst; (b) providing a second stream containing methanol and ethanol to said process; (c) feeding said second stream to said reactor whereby a portion of said isoamylenes is reacted with a portion of said methanol and a portion of said ethanol to produce a fourth stream containing tertiary amyl methyl ether, tertiary amyl ethyl ether, unreacted methanol and unreacted isoamylenes; (d) feeding said fourth stream along with a fifth stream comprising methanol and ethanol to a distillation column reactor containing a second fixed bed acid cation exchange resin in the form of a catalytic distillation structure wherein a substantial portion of said unreacted isoamylenes is reacted with methanol and ethanol to form additional tertiary amyl methyl ether and tertiary amyl ethyl ether while concurrently separating by fractional distillation unreacted methanol and ethanol from tertiary amyl methyl ether and tertiary amyl ethyl ether, said tertiary amyl methyl ether and said tertiary amyl ethyl ether being removed from said distillation column reactor as bottoms and said unreacted methanol and unreacted methanol along with any unreacted C₅ 's are removed overheads; (e) measuring the concentration of oxygen derived from alcohol in said distillation column reactor directly below said second fixed bed; and (f) controlling the concentration of oxygen derived from alcohol in said distillation column directly below said second fixed bed in the range of at least 0 weight % to 7 weight % at above the level whereby a full alcohol azeotrope is formed in the overhead and below the level whereby alcohol is present in the bottoms. 